Textile treatment composition

ABSTRACT

Textiles, particularly carpets, are endowed with oil and water repellency and soil resistance by treatment thereof with certain detergent-compatible fluorochemical compounds which can also be used in conjunction with anionic or nonionic detergents to provide cleaning/treating compositions for cleaning such textiles simultaneously with the treatment. The textile treating compositions of the invention comprise certain detergent-compatible fluorochemical compounds which are dissolved and/or dispersed in a suitable liquid vehicle. The textile treating/cleaning compositions of the invention also contain an anionic and/or a nonionic detergent.

BACKGROUND OF THE INVENTION

This invention relates to textile treatment with novel compositions toimpart water and oil repellency and soil resistance. In another aspect,the invention relates to cleaning/treating compositions for cleaningsuch textiles simultaneously with such treatment.

DESCRIPTION OF THE PRIOR ART

The treatment of textiles with fluorochemicals to impart water and oilrepellency has been known for some time. As disclosed in U.S. Pat. Nos.3,068,187; 3,256,230; 3,256,231; 3,277,039; and 3,503,915, fluorinatedpolymers have been mixed with non-fluorinated polymers to obtain atreating composition which will impart water and oil repellency totextiles, paper and leather. Such prior art compositions, however, aregenerally designed for initial factory treatment of the textile and arenot suited for use after the textile article has been soiled in use.

U.S. Pat. No. 3,377,197 discloses treating previously cleaned textilefabric, leather, rugs, etc., with fluorine-containing organometalliccompounds to impart resistance against soiling, staining and wetting.U.S. Pat. No. 3,382,097 discloses a treatment for imparting oil and soilrepellency to textile fabric, leather, rugs, etc., by treating with asolution of certain fluorinated organic carboxylic acids. This referencealso suggests combining a detergent with a fluorochemical acid in anaqueous medium for a one-step cleaning and treating operation, but itdoes not impart water repellency. And, although Netherlands patentapplication No. 6,606,734 suggests dispersing an insoluble fluorocarboncompound in a laundering composition useful for a two-step cleaningoperation, such disclosure does not provide a one-part treating/cleaningcomposition.

Other prior art cleaning compositions, such as carpet shampoos, do notimpart water and oil repellency. Rather, many such conventional cleaningcompositions leave hydrophilic or oleophilic residues on the cleanedsubstrate which actually attract and hold dirt. Although some cleaningcompositions contain ingredients designed to impart soiling resistance,such compositions do not impart water and oil repellency.

SUMMARY OF THE INVENTION

The present invention provides novel compositions for the fluorochemicaltreatment of textiles such as carpets, upholstery and the like, toimpart water and oil repellency and stain resistance thereto. Quitesurprisingly, these novel compositions can also contain detergent andthereby clean and impart repellent properties in one operation.

In accordance with the invention, a textile treatment is provided bycertain detergent-compatible organic fluorochemical compounds. Thetextile treating compositions of the invention comprise certaindetergent-compatible fluorochemical compounds which are dissolved and/ordispersed in a suitable liquid vehicle. The textile treating/cleaningcompositions of the invention also contain an anionic and/or a nonionicdetergent. The term "detergent compatible" is used herein to denote thatthe organic fluorochemical compounds are physically and chemicallyunaffected by anionic and non-ionic detergents at concentrations thereoftypically encountered in textile cleaning solutions, and thus capable ofbeing applied during a cleaning operation. Additionally, the organicfluorochemical compound treatment, applied to a substrate such as acarpet, can be cleaned with conventional carpet-cleaningdetergent-containing solutions without removing or rendering ineffectivethe organic fluorochemical, provided that excessive detergent residuedoes not remain.

DETAILED DESCRIPTION

The detergent-compatible organic fluorochemical compounds that areuseful in the invention are those in which a fluorinated, preferablysaturated, aliphatic radical is linked to a non-fluorinated organicradical which bears at least one carboxylic acid group which may beneutralized. The non-fluorinated organic radical has at least 6 members(e.g., carbon atoms) in a skeletal backbone structure which links thefluoroaliphatic radical to the carboxylic acid group. This skeletalstructure can include catenary oxygen and/or trivalent nitrogen heteroatoms, providing a stable linkage between the fluoroaliphatic radicaland the carboxylic acid group. These fluorochemical compounds arecapable of dissolving in an organic solvent, preferably in awater-soluble or water-dispersible organic solvent.

The fluoroaliphatic radicals, hereinafter called "R_(f) radicals", aresaturated, and generally monovalent aliphatic moieties. They can bestraight chain, branched chain, and, if sufficiently large, cyclic, orcombinations thereof, such as alkylcycloaliphatic radicals. Thefluoroaliphatic skeletal chain can include catenary oxygen and/ortrivalent nitrogen hetero atoms bonded only to carbon atoms, such heteroatoms providing stable linkages between fluorcarbon groups and notinterfering with the inert character of the R_(f) radical. While R_(f)can have a large number of carbon atoms, R_(f) radicals having no morethan 20 carbon atoms will be adequate and preferred since largerradicals usually represent a less efficient utilization of fluorine thanis possible with smaller R_(f) radicals. Generally, R_(f) will have 3 to20 carbon atoms, preferably 6 to about 12, and will contain 40-78 weightpercent, preferably 50-77 weight percent, carbon-bonded fluorine. Theterminal portion of the R_(f) radical has preferably at least one fullyfluorinated carbon atom, e.g., CF₃, and the preferred R_(f) radical issubstantially completely, or fully fluorinated, as in the case whereR_(f) is perfluoroalkyl, C_(n) F_(2n+1).

Generally, the detergent-compatible organic fluorochemical compoundswill contain about 10 to 60 weight percent, preferably about 15 to 45weight percent, of carbon-bonded fluorine. If the fluorine content isless than about 10 weight percent, these compounds may no longer bedetergent compatible, while fluorine contents greater than about 60weight percent will require compounds which are uneconomical to use.

Suitable liquid vehicles for the compositions of the invention willdissolve or disperse the detergent-compatible fluorochemical. Thepreferred liquid vehicles are organic solvents or organic solvent/watermixtures. The organic solvents for this purpose are volatile at roomtemperature and will preferably be capable of dissolving and/ordispersing 1 part detergent-compatible fluorochemical compound per 10parts organic solvent and preferably will dissolve and/or disperse inwater at least 1 part organic solvent per 10 parts water. The organicsolvents are non-toxic, do not have an odor which is objectionable tothe normal person and do not harm carpet fibers or structure.

Organic fluorochemical compounds which are detergent compatible andpreferred in the present invention have the structure: (R_(f) Q)_(e)(XCO)_(m) A(COOM)_(p) wherein R_(f) is fluorinated aliphatic radical asdescribed above, "Q" is a divalent linking group, "M" is a cationselected from NH₄ ⁺, Na⁺, K⁺, Li⁺, H⁺, or a protonated alkyl aminehaving from 1-6 carbon atoms in the alkyl group, "A" is a polyvalentorganic radical having a valency of m+p and is preferably derived from apolybasic organic acid or an organic anhydride, "X" is NR (wherein "R"is hydrogen or a lower alkyl group of from 1 to 14 carbon atoms),

.Iadd.or .Iaddend.N .[.or O.]. "e", "p" and "m" are integers of 1 or 2.

It should be noted that because of the polyvalent nature of the "A"group, the fluorochemical compounds may be a polyanhydride polymerstructure having repeating structure ##STR1## wherein "R" is alkyl offrom 1-6 carbon atoms or alkoxy alkyl such as butoxyethyl, ethoxyethyl,etc, z is from zero to 1, b is from zero to 10 times a and a plus b isan integer representing the number of repeating units in the polymer.

The divalent linking group "Q" has a valency of 2 and may include one ormore groups such as alkylene [--(CH₂)_(n) --], sulfonamido alkylene[--SO₂ NR(CH₂)--], alkylene carboxyloxy alkylene [--(CH₂)_(n) COOCH₂ CH₂--], and sulfonamido alkylenoxy alkylene [--SO₂ NR(CH₂ CH₂ O)_(n) CH₂CH₂ --]wherein "R" is hydrogen or a lower alkyl group having from about1 to 14 carbon atoms and n is an integer from about 1 to 15.

The polyvalent organic radical "A" has, as previously mentioned, avalency of m to p and may be aromatic, araliphatic, cycloaliphatic orheteroaromatic and is preferably the residue of a polybasic acid or ananhydride from which the carboxyl groups have been deleted. Suchanhydrides and acids include maleic, succinic, phthalic,tetrachlorophthalic, chlorendic, tetrabromophthalic, 3-nitrophthalic,4-nitrophthalic, cis 1,2-cyclohexane dicarboxylic, 5-norbornene-2,3-dicarboxylic, 1,8-naphthalene dicarboxylic and benzophenonetetracarboxylic and others.

The detergent-compatible organic fluorochemical compounds describedabove and useful in the present invention may be prepared in any of avariety of ways. Most conveniently, the compounds which are preferred inthe invention are prepared by reacting a precursor fluorochemical amine.[.or alcohol.]. with a suitable anhydride. Precursor amines .[.andalcohols.]. will have the structure R_(f) QXH where "R_(f) ", "Q" and"X" are as described above. Useful illustrative examples of suchprecursor amines .[.and alcohols.]. include:

.[.CF₃ (CF₂)₇ SO₂ N(CH₃)CH₂ CH₂ OH.].

.[.CF₃ (CF₂)₃ SO₂ N(CH₃)CH(CH₃)CH₂ OH.].

.[.CF₃ (CF₂)₃ SO₂ N(CH₂ CH₃)CH₂ CH₂ OH.].

.[.CF₃ (CF₂)₃ SO₂ N(CH₃)CH₂ CH(CH₃)OH.].

.[.CF₃ (CF₂)₇ SO₂ N(CH₂ CH₃)CH₂ CH₂ OH.].

.[.CF₃ (CF₂)₉ SO₂ N(CH₂ CH₂ CH₃)CH₂ CH₂ OH.].

.[.CF₃ (CF₂)₇ SO₂ N(CH₂ CH₂ CH₃)CH₂ CH₂ OH.].

.[.CF₃ (CF₂)₇ SO₂ N(C₂ H₅)(CH₂)₆ OH.].

.[.CF₃ (CF₂)₇ SO₂ N(C₂ H₅)(CH₂)₁₁ OH.].

.[.CF₃ (CF₂)₇ SO₂ N(C₄ H₉)(CH₂)₄ OH.].

.[.CF₃ (CF₂)₇ SO₂ N(CH₃)(CH₂)₄ OH.].

CF₃ (CF₂)₇ SO₂ N(CH₂ CH₃)CH₂ CH₂ NH₂

[CF₃ (CF₂)₇ SO₂ N(CH₂ CH₃)CH₂ CH₂ ]₂ NH

CF₃ (CF₂)₇ SO₂ N(CH₂ CH₃)CH₂ CH₂ N(CH₃)H

.[.CF₃ C₆ F₁₀ C₂ F₄ SO₂ N(CH₃)CH₂ CH₂ OH.].

.[.C₂ F₅ O(C₂ F₄ O)₃ CF₂ CONHC₂ H₄ OH.].

.[.CF₃ (CF₂)₇ SO₂ N(C₃ H₇)CH₂ OCH₂ CH₂ CH₂ OH.]. ##STR2## .[.CF₃ (CF₂)₆SO₂ CH₂ CH₂ OH.].

.[.CF₃ (CF₂)₆ COCH₂ CH₂ OH.].

.[.C₇ F₁₅ CON(C₂ H₅)C₂ H₄ OH.].

.[.C₈ F₁₇ SO₂ N(C₄ H₉)CH₂ CH₂ OH.].

.[.C₇ F₁₅ CON(CH₃)CH₂ CH₂ OH.].

.[.C₈ F₁₇ SO₂ NH(CH₃)(CH₂)₄ OH.].

.[.C₈ F₁₇ SO₂ N(CH₃)(CH₂)₁₁ OH.].

.[.C₆ F₁₃ SO₂ NCH₃ (CH₂)₄ OH.]. ##STR3## C₇ F₁₅ CH₂ NH₂ C₈ F₁₇ SO₂ N(C₄H₉)CH₂ CH₂ NH₂ ##STR4## C₈ F₁₇ SO₂ N(C₂ H₅)CH₂ CONHCH₂ CH₂ NH₂

C₈ F₁₇ SO₂ N(C₂ H₅)CH₂ CH₂ NHCH₂ CH₂ NH₂

Many of the precursor fluorochemical amines .[.and alcohols.]. are wellknown and/or commercially available. U.S. Pat. No. 3,346,612 discloses amethod of preparing the fluorochemical amines while U.S. Pat. No.3,398,182 discloses some useful amines .[.and alcohols.]..

In the reaction which produces the preferred detergent-compatibleorganic fluorochemical compound, the precursor fluorochemical amine.[.or alcohol.]. is reacted usually with about an equivalent amount ofthe anhydride. In certain instances, e.g., the polyanhydride polymerspreviously mentioned, the ratio (by equivalents) of amine .[.oralcohol.]. to anhydride may vary between 1:10 and 1:1. This reaction ismost conveniently accomplished in a solvent for both the reactants andthe reaction product. Typical solvents for the precursor fluorochemicalamine are water miscible and include dimethyl formamide, dimethylacetamide and N-methyl pyrrolidone, ketones such as acetone or methylethyl ketone, ethers such as tetrahydrofuran, and alkoxy ethanols, suchas 2-ethoxy ethanol or 2-butoxy ethanol (e.g."Butyl Cellosolve")..[.Preferred solvents for the precursor alcohols are aprotic and includedimethyl formamide dimethyl formamide, dimethyl acetamide, N-methylpyrrolidone, pyridine and triethylamine..].

When the precursor .[.alcohol or.]. amine is dissolved in an aproticsolvent, a minimum amount thereof to dissolve the reactants is used,since these solvents are generally removed before using the reactionproduct in a textile treatment.

The dissolved precursor fluorochemical amine is typically reacted withthe anhydride by slowly adding the latter to a solution of the formerwith sufficient agitation to obtain uniform dispersal. Reaction timesare relatively short and the reactions are typically carried out attemperatures in the range of about 20°-80° C. and at atmosphericpressures. An ambient (air) reaction atmosphere may be used but drynitrogen is preferred.

It has been found that if the reaction temperatures are maintainedbetween about room temperature (20° C.) and 80° C., a high yield of thedesired organic fluorochemical compound is produced with minimal sideproducts from secondary reaction. If the temperature is elevated about85° C., some reaction of the anhydride and solvent may occur or theamide may partly cyclize, reducing the water solubility of the resultantcompounds which may be undesirable in some instances.

.[.Fluorochemical alcohols may be reacted with the anhydride by directmelt esterification or in the presence of aprotic solvents, preferablywith esterification promoting catalysts such as perfluoromethanesulfonic acid or a tertiary amine..].

Once the reaction has been completed to produce the desireddetergent-compatible fluorochemical compound, if the solvent used isundesirable for the final water dilution (because of being slow drying,having a bad odor, etc.), the product may be removed from the reactionsolvent for example by precipitating it therefrom with an aqueous acidsolution. The precipitate is then dissolved and/or dispersed in theliquid vehicle.

The resultant fluorochemical compound product, which has a freecarboxylic acid group, may be neutralized with a slight excess of a baseto make it water-soluble or water-dispersible. Suitable bases for thispurpose are at least moderately water-soluble and include ammonia,potassium hydroxide, sodium hydroxide, morpholine or an alkylamine suchas triethylamine, propylamine, ethylamine, isopropylamine,isobutylamine, butylamine, ethanolamine, diethanolamine,diethylaminoethanol, 2-amino-2-ethyl propanol, etc.

The term "dispersible" as used herein means that the ingredients of themixture either are mutually soluble, or otherwise stably dispersible,e.g., forming a colloidal suspension in water at the desiredconcentration.

The organic solvent either dissolves the acidic fluorochemical compoundsor aids in the water-dispersibility of the neutralized fluorochemicalcompound, providing aqueous treating or treating/cleaning compositionswhich are preferred. The preferred ratio of organic fluorochemicalcompound to organic solvent is on the order of 1:1 to 1:5, by weight.Organic solvents which may be utilized include ethanol, alkoxyethanolssuch as 2-ethoxy or 2-butoxy ethanol, tetrahydrofuran, methyl ethylketone, acetone, dimethyl formamide etc, and mixtures thereof. Organicsolvents having no or limited water-solubility, e.g., hexoxy ethanol,may be used in minor proportions with organic solvents which are morewater-soluble.

The solutions of fluorochemical compound, water and solvent describedabove, when applied to clean or previously cleaned textile materials anddried, provide a high degree of water and oil repellency and soilresistance. Not only is such repellency provided, but the treatedtextile may be subsequently cleaned with common detergent-containingtextile cleaing solutions and still thereafter retain these repellencyproperties if most of the detergent is removed (e.g., by means ofwet-vacuuming).

Typical concentrations of the organic fluorochemical compound will be onthe order of about 10 to 25 weight percent by weight fluorochemicalcompound per total weight of a concentrated solution, depending upon itssolubility. For use, the concentration of organic fluorochemicalcompound will be on the order of 1 to 2% by weight. Excellent water andoil repellency and stain resistance are obtained on carpeting having anadd-on weight of at least 1 g per sq. meter of fluorochemical compound,preferably 2-5 grams per sq. meter.

It should be noted that certain of the detergent-compatiblefluorochemical compounds of the invention, i.e., where "X" in thegeneral formula noted above is nitrogen, will be endowed with improvedrepellency properties upon being heated at an elevated temperature,e.g., over 100° C., preferably at about 125° C. One example is thefluorochemical compound produced as described above by reacting adicarboxylic anhydride and a primary fluorochemical amine, as the acidor neutralized with base such as ammonia or morpholine. Heating timessufficient to note this improvement will typically be between 10 minutesand 5 hours. This further treatment may be accomplished on the textilesurface during its production, by treating the textile with the treatingcompositions described above and by heating the treated textile.

As previously mentioned, the solution may be a cleaning/treatingcomposition containing a detergent. The detergents should bewater-dispersible at concentrations of at least 1% by weight. Detergentswhich are useful in such compositions are nonionic or anionic detergentswhich dry to a non-oily, non-tacky residue from an aqueous medium. Soliddetergents which leave a dry residue are desirable. Cationic detergentsare not useful because they are not generally compatible with the otheringredients in the compositions.

Useful anionic detergents include alkali metal or ammonium salts offatty acids (e.g., 12 carbons or more), alcohol sulfates (orsulfonates), alcohol phosphates (or phosphontes), alkyl sulfonates,alkyl phosphates (or phosphonates), polyoxyalkylene alcohol sulfates (orsulfonates), polyoxyalkylene alkyl carboxylates, and polyoxyalkylenealcohol phosphates (or phosphonates).

Examples of commercial anionic detergents that are useful in theinvention include sodium lauryl sulfate (commercially available underthe trade designation "Avirol" 101), potassium lauryl sulfate(commercially available under the trade designation "Culverol" KLS),magnesium lauryl sulfate (commercially available under the tradedesignation "Culverol" MgLS), sodium myristyl sulfate (commerciallyavailable under the trade designation "Maprofix" MSP90), sodium cetylsulfate (commercially available under the trade designation "Conco"Sulfate A), sodium tridecyl sulfate (commercially available under thetrade designation "Sipex" TDS), sodium 7-ethyl-2-methyl-4-undecylsulfate (commercially available under the trade designation "Tergitol"4). Of these, sodium lauryl sulfate is the preferred detergent.

Nonionic detergents, either by themselves or in conjunction with anionicdetergents, can also be used in the cleaning/treating compositions. Whennonionic detergents are used, it is preferred that they be normallysolid materials, or if not solid, that they be used in amounts less thanabout 20% by weight of the total solids in the cleaing/treatingsolution. Useful commercial nonionic surfactants include "Igepal DM-970"and "Pluronic F 68".

The weight ratio of detergent to organic fluorochemical compound is onthe order of 1:1 to 2:1, by weight. At more than 2:1 detergent toorganic fluorochemical compound, some reduction in the water repellencyproperties of carpet treated with the organic fluorochemical compoundmay be noted.

The treating or cleaning/treating composition of the invention maycontain other ingredients which increase effectiveness or improvephysical appearance. For example these compositions may contain anadditional known anti-redeposition agent. A typical example of such ananti-redeposition agent is the ammonium salt of the hydrolyzed copolymerof styrene and maleic anhydride. Other useful anti-redeposition agentsinclude polyvinyl pyrolidone and water dispersible acrylate copolymers.Other optional additives include germicidal materials, perfumes and thelike.

In use, the diluted cleaning/treating compositions are typically appliedto the surface being cleaned and treated using conventional equipment.For example, for carpet cleaning, a conventional scrubbing device, whichmay be fitted with a liquid dispenser, is used, the cleaning/treatingsolution being dispensed from such a dispenser. The cleaning/treatingand the treating solutions of this invention may be sprayed upon thesurface to be cleaned and/or treated by conventional spraying devices oras an aerosol. The aerosol dispensing container will contain the desiredsolution and sufficient aerosol propellent to dispense the solution.Such propellents are typically low boiling chloro-, fluoro-substitutedalkanes (e.g., "Freon 12") or low boiling alkanes or mixtures thereofsuch as a mixture of isobutane and propane.

Compositions according to the invention are applied to various textilesubstrates, typically carpeting of synthetic fibers, and the treatedsubstrates were evaluated for oil and water repellency, as follows:

OIL REPELLENCY TEST

The test for oil repellency (which is similar to the method described inAATCC Test No. 118-1966T) involves wetting the fabric by a selectedseries of liquid hydrocarbons of different surface tensions. The testliquids are as follows:

    ______________________________________                                        Oil Repellency                                                                Rating Number                                                                              Test Liquid                                                      ______________________________________                                        1            "Nujol"                                                          2            65 35 "Nujol" n-hexadecane by volume                             3            n-hexadecane                                                     4            n-tetradecane                                                    5            n-dodecane                                                       6            n-decane                                                         7            n-octane                                                         8            n-heptane                                                        ______________________________________                                    

"Nujol" is the trademark of Plough, Inc., for a mineral oil having aSaybolt viscosity 360/390 at 38° C. and a specific gravity 0.880/0.900at 15° C.

In the test, one test specimen, approximately 20×20 cm, is conditionedfor a minimum of four hours at 21±1° C. and 65±2% relative humidityprior to testing. The test specimen is then placed on a smooth,horizontal surface and, beginning with the lowest-numbered test liquid,a small drop--approximately 5 mm in diameter (0.05 ml. volume)--isplaced with a dropping bottle pipette on the test specimen in severallocations. The dropping bottle pipette is a 60 ml. dropping bottle witha ground-in pipette and "neoprene" rubber bulb. (Prior to use, the bulbshould be soaked in heptane for several hours and rinsed in freshheptane to remove soluble substances). The drop is observed for 30seconds at an angle of approximately 45°.

If no penetration or wetting of the fabric at the liquid-fabricinterface and no wicking around the drop occurs, a drop of the nexthigher-numbered test liquid is placed at a side adjacent on the fabricto the first drop, again observing the drop for 30 seconds. Thisprocedure is continued until one of the test liquids shows obviouswetting of the fabric under or around the drop within 30 seconds. Anuntreated nylon tufted pile carpet has an oil repellency of zero. Thesame carpeting treated with the treatment of the invention has an oilrepellency up to 6.

WATER REPELLENCY TEST

The treated carpet is tested for water repellency, after it is dried forat least 4 hours at room temperature (about 20° C.) and under ambientlaboratory humidity conditions (about 55% relative humidity).

One drop of room temperature tap water (about 2-3 mm in diameter) isthen carefully applied utilizing an eye dropper held about 1 cm from thefiber surface which will receive it. The test is repeated on an adjacentarea with a drop of an isopropyl alcohol/water solution (10/90% byweight). The drop is observed and one of the following ratings given,depending upon the observations:

    ______________________________________                                        Rating  Observations                                                          ______________________________________                                        excellent                                                                             The water drop does not wet the surface and                                   remains almost spherical in shape for at least                                2 hours. The isopropyl alcohol/water solution                                 drop remains on the fiber surface for at least                                1 hour                                                                good    The water drop remains on the fiber surface                                   for at least 1 hour with practically no wetting                               although the shape may not be spherical. The                                  isopropyl alcohol/water solution remains at                                   least 10 minutes before penetrating the fiber                         fair    The water drop may wet the upper surface of                                   the fiber but does not substantially penetrate                                the bulk of the carpeting for at least 1 hour                                 The isopropyl alcohol/water solution penetrates                               the bulk of the carpeting almost immediately                          poor    Both the water and the alcohol solution                                       immediately penetrate the bulk of the carpet                          ______________________________________                                    

Untreated nylon carpeting samples generally have a poor to fair waterrepellency while the same carpet treated with compositions according tothe invention have a water repellency of fair to excellent. The fairrating of an untreated carpet, typically temporary, is usually caused byoily residues which are usually on a new carpet surface. A permanentfair water repellency is acceptable for a carpet treatment.

The invention is illustrated by the following examples, wherein allparts are by weight unless otherwise specified.

EXAMPLE 1

The organic fluorochemical compound ##STR5## was prepared by reactingtetrachlorophthalic anhydrice (hereinafter called "TCPA" and sold underthe trade designation "Tetrathal") with the fluorochemical amine,m-aminophenol-perfluorooctane sulfonate, ##STR6## and neutralizing withammonia. Twenty-five parts of TCPA was suspended in 75 parts of dimethylformamide, the suspension heated to about 50° C. and 5 parts oftriethylamine added, producing a reddish-brown color. Next, 50 parts ofthe fluorochemical amine was added with mixing and continued heating at50° C. producing a clear solution which was cooled to room temperature.The slightly soluble monocarboxylic acid derivative was produced andisolated by diluting the clear solution with about 6 volumes of diluteacetic acid solution, causing this derivative to precipitate as a whitesolid. The precipitate was filtered, washed with distilled water and airdried at room temperature.

The desired organic fluorochemical compound treatment concentrate wasprepared by dissolving and neutralizing the acid derivative (about 1.0part) in a solution consisting of 0.5 parts ammonia, 3.0 parts "ButylCellosolve" and 5.5 parts water.

This treatment concentrate was dilued with about nine volumes of waterand the resultant solution was applied to a previously cleaned, rinsedand dried 2 foot square tufted looped pile nylon carpet test sample andpermitted to dry overnight, producing a dried add-on weight of 5.4grams/m². The treated carpet, when tested for oil and water repellencyas described above, had an oil repellency of 5 and a water repellencyrating of "excellent".

EXAMPLE 2

18 parts of TCPA was reacted with 50 parts of fluorochemical amine,m-aminophenol-perfluorooctane sulfonate. The fluorochemical amine wasmixed with 130 parts of "Butyl Cellosolve" in the reaction flask and themixture heated to about 60° C. until clear. Then the TCPA was added inone lot and the mixture heated to about 70° C. with continued stirring.When the reaction mixture became clear, heat was discontinued and 20parts of ammonium hydroxide solution (28% NH₃) was added followedimmediately by a mixture of 330 parts of deionized water and 10 parts ofchelating agent solution ("Versenol-120") with stirring ("Versenol 120"is water solution containing 41.0% trisodium salt of N-hydroxy-ethylethylene diamine triacetic acid). Then, 300 parts of a 10% by weightaqueous solution of styrene/maleic anhydride copolymer ("SMA-3000"),hydrolyzed with ammonia, anti-redeposition agent was added followed by130 parts of detergent solution ("Richonol A", 30% sodium laurylsulfate), 5 parts of fluorochemical surfactant ("FC 128") with heatingto about 95°, giving a clear cleaning/treating concentrate to which wasadded 0.5 part IFF 5009-S fragrance.

The concentrate was diluted 16 times with water to make acleaning/treating composition. Soiled tufted loop pile nylon carpetingcleaned with this composition shows oil repellency of 3, a "good" waterrepellency and excellent soiling resistance. A carpet sample as cleanedand treated with the composition of this example and an identical carpetsample was cleaned and treated with a control composition which lackedthe fluorochemical amine adduct. When both test samples were placed in aheavy pedestrian traffic situation, examination after one week showedthe carpet treated according to the invention to be cleaner.

EXAMPLE 3

The fluorochemical amine, m-aminophenol-perfluorooctane sulfonate, (50parts) was dissolved with stirring in 140 parts "Butyl Cellosolve" at60° C., producing a clear solution. Then 25 parts TCPA was added withstirring and heating to 80° C. until reaction was complete. The reactionmixture was reduced in temperature to 60°-65° C. and 20 partsconcentrated ammonium hydroxide (28% NH₃) was added followed immediatelyby 430 parts of deionized water and 4 parts of "Versenol 120" chelatingagent solution. A clear solution was obtained, to which was added 150parts "Richonol A" detergent, 657 parts of 10% styrene maleic acidcopolymer ("SMA 3000") ammonium salt solution in water, 6 partsfluorochemical surfactant "FC-128", 1.5 part fragrance, and watersufficient to bring the total to 1500 parts.

One part of the resultant composition was diluted with two partsdistilled water to give a solution which was placed in a conventional 12ounce aerosol can with about 10% by weight of isobutane aerosolpropellent. The aerosol shampoo was sprayed upon the surface of a 2×2ft. soiled test sample of nylon carpeting, and the carpet cleaned byutilizing a sponge mop applicator to work the carpet surface. Anothersoiled carpet sample, the same type and size, was cleaned in the samemanner with a prior art composition known as "New Johnson's Glory". Bothcleaned samples were dried, and placed in a heavy pedestrian trafficsituation. After one week, the sample treated with the compositionaccording to the invention was considerably cleaner than that treatedwith the "New Johnson's Glory". Upon subsequent cleanings, the carpettreated according to the invention cleaned much easier than the carpettreated with the "New Johnson's Glory".

EXAMPLE 4

50 parts of m-aminophenol-perfluorooctane sulfonate was first dissolvedin 140 parts of "Butyl Cellosolve" at 60° C. and 18 parts TCPA was addedwith continued stirring and heating to about 80° C. until the reactionwas complete. The reaction mixture was cooled to about 60°-65° and 20parts concentrated ammonium hydroxide solution (28% NH₃) was addedfollowed immediately by 218 parts deionized water, 337.5 parts 10%solution of styrene/maleic anhydride copolymer ("SMA 3000") hydrolyzedwith ammonia, 135 parts "Richonol" A detergent, 4.5 parts fluorochemicalsurfactant ("FC 128") and 18.0 parts organic solvent ("Super HiflashNaphtha"), producing a cleaning/treating concentrate.

Two 30 cm by 65 cm new nylon carpet test samples from the same carpetlot were cleaned, one sample with 100 ml of "CHEMSPEC 161" soilretardant carpet shampoo at the recommended dilution of 16:1 and theother sample with a solution consisting of 1 part of the concentratedescribed above and 8 parts water. After drying, the two samples wereused in a heavy pedestrian traffic situation for over 2 weeks. Thesample cleaned with composition of the invention described above had a"good" water repellency, and an oil repellency of 4 and appeared cleanerboth before and after vacuuming than the sample cleaned with the"CHEMSPEC No. 161" rug shampoo.

After vacuuming, equal amounts of the following common household itemswhich cause stains were applied over each treated carpet sample in theorder shown:

red dyed vegetable oil

salad dressing

mustard

ketchup

These household items were allowed to stand on the carpet samples forover one hour, and then the excess was carefully removed with a spatulaand the carpet surface blotted with an absorbent cloth. The remainingresidue was removed by shampooing one test sample with 100 ml of asolution consisting of 1 part "CHEMSPEC 161" shampoo concentrate and 16parts water. Immediately after cleaning both carpet samples appeared tobe free of stains, but after drying at room temperature for about 12hours, the sample shampooed with the composition of the inventionappeared cleaner than the sample shampooed with the "CHEMSPEC 161"shampoo.

When the dried samples were placed in a heavy pedestrian trafficsituation for 24 hours, severe soiling was noticed on the "CHEMSPEC 161"cleaned sample, especially in the areas stained as described above. Thesample treated with the composition of this example looked clean overits entire surface with the exception of a very small portion of thearea where the salad dressing stain had been placed. Fifteen days laterthe sample treated with the composition of this example was dramaticallycleaner than the other sample.

EXAMPLE 5

"Butyl Cellosolve" (140 parts) and 50 parts of m-aminophenolperfluorooctane sulfonate were charged in a 3 neck flask fitted with amechanical stirrer, thermometer and heating mantle, the contents raisedto 60° C. with stirring until they became clear. Then, 25 parts TCPA wasadded with continued stirring and heating to about 80° C., maintainingthis temperature until the solution became clear. The temperature of theflask contents was then lowered to about 60°-65° and 20 partsconcentrated ammonium hydroxide solution (28% NH₃) was added, followedimmediately by 521 parts deionized water, 4 grams of "Versenol 120"chelating agent solution and 0.5 part fragrance, producing a treatmentconcentrate.

EXAMPLE 6

Four 12×12 inch samples of new nylon tufted loop pile carpet (identifiedas A-D herein) were sprayed with a test solution consisting of 50 gramsof the solutions diluted as shown below. The solutions consisted of 1part of the concentrate of Example 5 diluted with the amount of watershown in the following table.

    ______________________________________                                        Carpet Sample   Volumes of Water                                              ______________________________________                                        A                4                                                            B               10                                                            C               20                                                            D               40                                                            ______________________________________                                    

After drying at room temperature, each of the treated carpet samples hadan oil repellency of 6 and "good" to "excellent" water repellency.

EXAMPLE 7

The concentrate of Example 5 was diluted with 4 volumes of water and theresultant solution was applied by means of an electric motor drivensprayer onto the surface of nylon loop pile carpet which had been usedfor some time as an entryway floor covering for the employee entrance ofa large office building, at about 320 g/m² solution, producing an add-onweight of about 6.4 g/m². The next day the carpet showed "excellent"water repellency and an oil repellency of 5-6. One month later (after anestimated pedestrian traffic of 60,000 pedestrian passes) waterrepellency was still "excellent" and oil repellency was 6 at the edgeand 4 in the main traffic lane.

EXAMPLE 8

The concentrate described in Example 5 was diluted 4 times with waterand the resultant solution was sprayed at 215 g/m² with a mechanicalsprayer over the surface of wool carpet which had been used for sometime in an executive office area, resulting, after overnight drying, ina dried add-on weight of 4.3 g/m². Initially, the carpet showed"excellent" water repellency and an oil repellency of 6. After twomonths of use the repellency results were unchanged.

EXAMPLE 9

The concentrate described in Example 5 was diluted 4 times with waterand the resultant solution was sprayed at 215 g/m² over the surface of anylon carpet which had been used for some time in a men's rest room in alarge office building, resulting in a dried add-on weight of 3.2 g/m².For up to 2 months later, the carpet showed "excellent" water repellencyand an oil repellency of 5. The more heavily used area of the carpet(near the entrance) showed an oil repellency of 2 and "good" waterrepellency.

EXAMPLE 10

150 parts "Butyl Cellosolve" was mixed with 50 parts of thefluorochemical amine, m-amino-phenol perfluorooctane sulfonate, at 50°C., until a clear solution developed. Then, 18 parts TCPA was added withcontinued mixing and heating to 70° C. until the resultant solutioncleared. Heating was discontinued and 26 parts concentrated ammoniumhydroxide (28% NH₃) was added with stirring, followed by a mixture of200 parts distilled water, 4 parts "Versenol-120", 340 parts 10%styrene/maleic anhydride copolymer "SMA-3000", ammonia neutralized,aqueous solution, 200 parts "Richonol A" detergent solution, 18 parts"Super Hi-flash Naphtha" organic solvent, 500 parts distilled water and4 parts fluorochemical surfactant ("FC-128"), giving a clearcleaning/treating solution.

One half of a 30 cm×60 cm sample of new nylon loop pile carpeting wasshampooed with 50 ml of Johnson's "Rugbee" shampoo at the recommendeddilution. The remaining half was shampooed with 50 ml of the solutiondescribed above. The carpet samples were allowed to dry overnight atroom temperature, then soiled artificially.

The artificial soiling involved securing carpet samples to the insidewalls of a cylinder which contains 100 small ceramic cylinders and asoiling formulation, and rotating the cylinder at 42 revolutions perminute for 20 minutes. The cylinder was 33.3 cm high and has an insidediameter of 24.9 cm. The carpet samples were ordinarily secured to theinside walls of the cylinder with double-coated pressure-sensitiveadhesive. The small ceramic cylinders were 1.9 cm by 1.9 cm in size andweighed about 23 grams each.

The soiling formulation used in the soiling test comprised:

    ______________________________________                                                              Parts                                                   ______________________________________                                        Peat Moss               70                                                    Gray Portland Cement (Type 1)                                                                         30                                                    Silica gel (200 mesh)   30                                                    Clay                    30                                                    Sodium chloride (about 80 mesh)                                                                       7                                                     Gelatin                 7                                                     Carbon black            23                                                    Red iron oxide          1                                                     Stearic acid            3.2                                                   Oleic acid              3.2                                                   Peanut oil              6                                                     Lanolin                 2                                                     ______________________________________                                    

The half treated according to the invention looked cleaner than theuntreated half both before and after vacuuming. Then each half again wasshampooed with 60 ml of the shampoos previously used and observationsmade. The half treated according to the invention cleaned easier andcleaner than "Rugbee"-treated half using the same technique and effort.When dried, the carpet half treated with the composition according tothe invention had a "good" water repellency and had an oil repellency of2-3. The remaining half cleaned with the Johnson's "Rugbee" had a "poor"water repellency and a zero oil repellency.

EXAMPLE 11

In this example isopropyl alcohol was used as the organic solvent andsodium hydroxide as the neutralizing base 200 parts of isopropyl alcoholand 50 parts of the fluorochemical amine described in Example 1 wereheated with stirring to about 60° C., and 25 TCPA were added withadditional stirring heating to 75° C. Within 30 minutes the mixturebecame clear, indicating completion of the reaction. After cooling theresultant solution to 50° C., 3.6 parts of sodium hydroxide in 50 partswater were added, followed by a mixture of 4 parts "Versenol 120", 0.5parts of fragrance and 283 parts of deionized water. The resultantsolution was heated to 75°-80° C. until a clear shampoo concentrate wasformed.

The concentrate was diluted with 10 volumes of water and the dilutedsolution sprayed on nylon carpet at about 540 g of spray/m² and thetreated carpet allowed to dry at room temperature. Repellency testingshowed water repellency to be "excellent" and an oil repellency of 6.

.[.EXAMPLE 12.].

.[.The fluorochemical compound active material in the carpet treatmentdescribed below was the ammonium salt of a half ester derived fromchlorendic anhydride and fluorochemical alcohol. Sixty parts of thefluorochemical alcohol, C₈ F₁₇ SO₂ N(C₂ H₅)CH₂ CH₂ OH, (0.1 mole), and50 parts of chlorendic anhydride (0.13 mole) were melted together at140°-150° C. for 30 minutes, producing a homogeneous glassy melt. "ButylCellosolve" (55 parts) was added to the melt and the mixture heated at140° C. for an additional 10 minutes with mixing. The mixture was cooledto 60°-65° and 30 parts concentrated ammonium hydroxide (28% NH₃) wasadded followed by 355 parts deionized water, producing a clear treatmentconcentrate which was diluted with 10 volumes of water for use..].

.[.The diluted treatment solution was applied to test samples of nylonand acrylic carpet (both looped pile construction), producing on each adried add-on weight of 5.4 g/m². After drying both test carpet samplesshowed "good" water repellency and an oil repellency of 4. Side by sideartificial soiling tests with control untreated carpet samples showedthe antisoiling ability of the treated carpet samples to be muchsuperior to that of the untreated controls..].

.[.EXAMPLE 13.].

.[.A carpet treatment based on the reaction product of a fluorochemicalamine and a fluorochemical alcohol with chlorendic anhydride in a onestep process. Thirty parts of the fluorochemical alcohol, C₈ F₁₇ SO₂N(C₂ H₅)CH₂ CH₂ OH, (0.05 mole) was placed in a 1,000 ml "Pyrex" glassflask equipped with a thermometer and stirrer and a heating mantle andheated to 100° C. with stirring. Fifty parts chlorendic anhydride (0.13mole) was added with continued stirring and heating to about 140° C. for30 minutes. Thereafter, the flask contents were cooled to 90° C. and asolution of 30 parts..]. ##STR7## .[.in 150 parts "Butyl Cellosolve"added, resulting in a reduction in temperature to 80° C. Aftermaintaining an 80° C. temperature about 10 minutes, the flask contentswere cooled to about 65° C. and 25 parts concentrated ammonium hydroxide(28% NH₃) added followed immediately by 315 parts of distilled water,producing a clear treatment concentrate which was diluted with 10volumes of water for use..].

.[.The diluted treatment was applied over the surface of an "Antron"nylon looped pile carpet sample, after drying providing a dried add-onweight of 5.4 g/m². The treated carpet had a "good" to "excellent" waterrepellency and an oil repellency of 4. Artificial soiling of the treatedcarpet sample and an untreated control revealed that the treated samplehad excellent antisoiling properties..].

EXAMPLES .Badd..[.14-56.]..Baddend. .Iadd.12-45 .Iaddend.

Textile treating compositions Examples 14-56 were prepared of materialsshown in the following table and tested for repellency on new tuftednylon carpeting which had been exhaustively cleaned. Shampooing was with"Triple S" rug and upholstery shampoo manufactured by StandardizedSanitation Systems, Inc. The shampooed carpet samples were dried at roomtemperature for at least 12 hours, cut into 7 to 10 cm wide strips,placed in a household automatic washing machine for full cycle utilizingwater only to rinse, and dried in a household dryer.

Before repellency testing, the stripped test samples had a zero oilrepellency and a "poor" water repellency. The treatments of Examples14-56, after being dried at room temperature for about 12 hours produceda dry add-on weight on the order of 3 to 6.5 grams per sq. m.

    __________________________________________________________________________                                                 Neutral-                         Reactants (moles)                       Reaction                                                                           izing                                                                             Organic                                                                            Repellency              Ex.  Fluorochemical        Acid or anhydride                                                                          solvent                                                                            base                                                                              solvent                                                                            Water Oil               __________________________________________________________________________    .[.14.]..Iadd.12.Iaddend.                                                           ##STR8##           1.0                                                                             tetrachlorophthalic anhydride                                                            1.0                                                                              IPA.sup.1                                                                          NaOH                                                                             BC.sup.2 IPA                                                                        excellent                                                                           5                .[.15.]..Iadd.13.Iaddend.                                                          "                   " tetrachlorophthalic                                                                        BC   NH.sub.3                                                                          BC    "    6                                            anhydride                                          .[.16.]..Iadd.14.Iaddend.                                                          "                   " tetrachlorophthalic                                                                        IPA  dieth-                                                                            IPA  fair  4                                            anhydride                                                                                       anol                                                                          amine                            .[.17.]..Iadd.15.Iaddend.                                                          "                   " tetrachlorophthalic                                                                        ethanol                                                                            NaOH                                                                              ethanol                                                                            excellent                                                                           5                                            anhydride                                          .[.18.]. .Iadd.16.Iaddend.                                                         "                   " tetrachlorophthalic                                                                        IPA  KOH IPA                                                     anhydride             BC    "    6                 .[.19.]..Iadd.17.Iaddend.                                                          "                   " tetrabromophthalic                                                            anhydride 1.0                                                                              BC   NH.sub.3                                                                          BC    "    4                 .[.20.]..Iadd.18.Iaddend.                                                          "                   " chorendic                                                                     anhydride 1.0                                                                              IPA  NH.sub.3                                                                          IPA   "    5                 .[.21.]..Iadd.19.Iaddend.                                                          "                   " chorendic    BC   NH.sub.3                                                                          BC    "    5                                            anhydride                                          .[.22.]..Iadd.20.Iaddend.                                                          "                   1.0                                                                             3-nitrophthalic            good.sup.4                                         anhydride 1.0                                                                              DMF.sup.3                                                                          NH.sub.3                                                                          BC.sup.2                                                                           fair  4                 .[.23.]..Iadd.21.Iaddend.                                                          "                   1.0                                                                             4-nitrophthalic       BC   good.sup.4                                                                          2                                            anhydride 1.0                                                                              BC   NH.sub.3                                                                          acetone                                                                            fair  5                 .[.24.]..Iadd.22.Iaddend.                                                          "                   0.9                                                                             1,2-cyclohexane                                                               dicarboxylic acid          good.sup.4                                         anhydride 1.0                                                                              BC   NH.sub.3                                                                          BC   fair  4                 .[.25.]..Iadd.23.Iaddend.                                                          "                   2.0                                                                             benzophenone tetra-                                                                             dietha-                                                     carboxylic acid   nol                                                         dianhydride                                                                             1.0                                                                              BC   amine                                                                             BC   excellent                                                                           5                 .[.26.]..Iadd.24.Iaddend.                                                          "                   1.0                                                                             norbornene dicarbox-                                                          ylic acid                                                                     anhydride 1.0                                                                              BC   NH.sub.3                                                                          BC   good  5                 .[.27.]..Iadd.25.Iaddend.                                                          "                   1.0                                                                             phthalic                   fair.sup.4                                                                          3                                            anhydride 1.0                                                                              DMF  NH.sub.3                                                                          IPA.sup.1                                                                          poor  4                 .[.28.]..Iadd.26.Iaddend.                                                          "                   1.0                                                                             naphthalic 1,8-dicar-                                                         boxylic acid               good.sup.4                                         anhydride 1.0                                                                              DMF  NH.sub.3                                                                          BC   poor  5                 .[.29.]..Iadd.27.Iaddend.                                                          "                   2.0                                                                             pyrromellitic                                                                 dianhydride                                                                   (PMDA)    1.0                                                                              DMF.sup.3                                                                          NH.sub.3                                                                          BC.sup.2                                                                           good  4                 .[.30.]..Iadd.28.Iaddend.                                                          "                   1.0                                                                             maleic                                                                        anhydride 1.0                                                                              DMF  NH.sub.3                                                                          IPA.sup.1                                                                          good.sup.4                                                                    poor  5                 .[.31.]..Iadd.29.Iaddend.                                                          "                   1.0                                                                             "SMA 1000".sup.5                                                                        2.0                                                                              BC   NH.sub.3                                                                          BC   good  3                 .[.32.]..Iadd.30.Iaddend.                                                          "                   1.0                                                                             "SMA 2000".sup.6                                                                        1.0                                                                              BC   NH.sub.3                                                                          BC   good  3                 31   .Iadd."             1.0                                                                             "SMA 2000"                                                                              2.0                                                                              BC   NH.sub.3                                                                           BC  excellent.sup.4                                                                      2                                                                      good.Iaddend.           .[.34.]..Iadd.32.Iaddend.                                                          "                   1.0                                                                             "SMA 3000".sup.7                                                                        1.0                                                                              BC   NH.sub.3                                                                          BC   excellent.sup.4                                                                     2                                                                       good                    .[.35.]..Iadd.33.Iaddend.                                                           ##STR9##           1.0                                                                             "Gantrez AN 139".sup.8                                                                   1.0                                                                              DMF  NH.sub.3                                                                          BC   good.sup.4                                                                          1 2              .[.36.]..Iadd.34.Iaddend.                                                          "                   1.0                                                                             TCPA      0.7                                                                              DMF  NH.sub.3                                                                          BC   excellent                                                                           5                 .[. 37.]..Iadd.35.Iaddend.                                                          ##STR10##          1.0                                                                             chlorendic anhydride                                                                    1.0                                                                              BC.sup.2                                                                           NH.sub.3                                                                          BC   good  5                 .[.38.]..Iadd.36.Iaddend.                                                          "                   1.0                                                                             tetrachloro-                                                                  phthalic              BC/                                                     anhydride 1.0                                                                              BC   NH.sub.3                                                                          acetone                                                                            good  4                 .[.39.]..Iadd.37.Iaddend.                                                          C.sub.8 F.sub.17 SO.sub.2 NHCH.sub.2 CH.sub.2 NH.sub.2                                            1.0                                                                             tetrachloro-                                                                            1.0                                                                              N-methyl                                                                           triethyl                                                    phthalic     pyroli-                                                                            amine                                                                             BC   good  4                                            anhydride    done                                  .[.40.]..Iadd.38.Iaddend.                                                          "                   1.0                                                                             chlorendic                                                                    anhydride 1.0                                                                              DMF.sup.3                                                                          NH.sub.3                                                                          BC   good  4                 .[.41.]..Iadd.39.Iaddend.                                                           ##STR11##          1.0                                                                             chlorendic  anhydride                                                                   1.0                                                                              BC   NH.sub.3                                                                          BC   good  1                 .[.42.]..Iadd.40.Iaddend.                                                          "                   1.0                                                                             tetrachloro-                                                                  phthalic                                                                      anhydride 1.0                                                                              BC   NH.sub.3                                                                          BC   good.sup.4                                                                          1                                                                       fair                    .[.43.]..Iadd.41.Iaddend.                                                          "                   2.0                                                                             tetrachloro-                                                                            1.0                                                                              BC   NH.sub.2                                                                          BC   good.sup.4                                                                          3                                            phthalic                                                                      anhydride                  fair  3                 .[.44.]..Iadd.42.Iaddend.                                                           ##STR12##          1.0                                                                             chlorendic anhydride                                                                    1.0                                                                              BC.sup.2                                                                           NH.sub.3                                                                          BC   excellent                                                                           4                 .[.45.]..Iadd.43.Iaddend.                                                           ##STR13##          1.0                                                                             "SMA 3000".sup.7                                                                        2.0                                                                              BC   NH.sub.3                                                                          BC   good  2                 .[.46.]..Iadd.44.Iaddend.                                                           ##STR14##          0.8                                                                             tetrachloro- phthalic anhydride                                                         1.0                                                                              BC   NH.sub.3                                                                          BC   excellent                                                                           5                 .[.47.]..Iadd.45.Iaddend.                                                           ##STR15##          1.0                                                                             "SMA 1000".sup.5                                                                        3.0                                                                              BC   NH.sub.3                                                                          BC   excellent .sup.4                                                              good  2                 .[.48                                                                               ##STR16##          1.0                                                                             chlorendic anhydride                                                                    1.25                                                                             none NH.sub.3                                                                          BC   good  2                 49                                                                                  ##STR17##          1.0                                                                             chlorendic anhydride                                                                    1.25                                                                             N-methyl pyroli- done triethyl-                                               amine                                                                              NH.sub.3                                                                          BC   fair  4                 50                                                                                  ##STR18##          1.0                                                                             cyclohexane 1,2- dicarboxylic acid anhydride                                            1.3                                                                              none NH.sub.3                                                                          BC.sup.2                                                                           fair  4                 51   "                   1.0                                                                             chlorendic                                                                    anhydride 1.25                                                                             N-methyl NH.sub.3                                                                           BC    good                                                   pyroli                                                                           done                                                                          triethyl-                                                                     amine                                 52                                                                                  ##STR19##          1.0                                                                             chlorendic anhydride                                                                    1.25                                                                             N-methyl                                                                           NH.sub.3                                                                          IPA.sup.1                                                                          good  2                                                         pyroli-                                                                       Done                                                                          triethyl-                                                                     amine                                 53                                                                                  ##STR20##          1.0                                                                             cyclohexane 1,2- dicarboxylic acid anhydride                                            1.3                                                                              N-methyl pyroli- triethyl-                                                         NH.sub.3                                                                          BC   fair  5                 54   "                   1.0                                                                             tetrachloro-                                                                  phthalic                                                                      anhydride 1.0                                                                              DMF.sup.1                                                                          NH.sub.3                                                                          BC   good  4                 55                                                                                  ##STR21##          1.0                                                                             "SMA 1000".sup.5                                                                        2.0                                                                              DMF  NH.sub.3                                                                          BC   excellent.sup.4                                                               fair  1 3               56   "                   1.0                                                                             "SMA 1000".sup.5                                                                        4.5                                                                              DMF  NH.sub.3                                                                          BC   fair  2.].              __________________________________________________________________________     .sup.1 isopropyl alcohol                                                      .sup.2 "Butyl Cellosolve"-                                                    .sup.3 dimethyl formamide                                                     .sup.4 dried in oven at 120° C.                                        .sup.5 styrene/maleic anhydride (1:1) copolymer                               .sup.6 styrene/maleic anhydride (2:1) copolymer                               .sup.7 styrene/maleic anhydride (3:1) copolymer                               .sup.8 copolymer of maleic anhydride and methyl vinyl ether              

What is claimed is:
 1. A composition comprising a liquid vehiclecontaining from about 1% to about 25% by weight of adetergent-compatible organic fluorochemical compound containing about 10to 60 weight percent carbon-bonded fluorine and having the formula(R_(f) Q)_(e) (XCO)_(m) A(COOM)_(p) where R_(f) is fluorinated aliphaticradical of at least three carbon atoms, "Q" is a divalent linking group,"M" is a cation selected from NH₄ ⁺, Na⁺, K⁺, Li⁺, H⁺ or is a protonatedalkyl amine having from 1-6 carbon atoms in the alkyl group "A" is apolyvalent organic radical having a valency of m+p and is the residue ofa polybasic organic acid or an organic anhydride, "X" is NR (wherein Ris hydrogen or an alkyl group of from 1 to 14 carbon atoms), .Iadd.or.Iaddend.N .[.or O.]. and e, p and m are integers of 1 or
 2. 2. Thecomposition of claim 1 wherein said liquid vehicle is a mixture of waterand sufficient compatible water-soluble organic solvent to dissolveand/or disperse said fluorochemical compound.
 3. The composition ofclaim 2 wherein said organic solvent is selected from the groupconsisting of 2-butoxy ethanol, isopropyl alcohol and ethyl alcohol. 4.The composition of claim 1 wherein "A" is the residue of chlorendicanhydride.
 5. The composition of claim 1 wherein said fluorochemicalcompound is ##STR22##
 6. The composition of claim 1 wherein R_(f) is C₈F₁₇ and M is K⁺, Na⁺ or NH₄ ⁺.
 7. A composition comprised of a liquidvehicle containing (1) from about 1% to about 25% of adetergent-compatible fluorochemical compound containing from about 10 toabout 60 percent carbon-bonded fluorine and having the formula (R_(f)Q)_(e) (XCO)_(m) A(COOM)_(p) where R_(f) is fluorinated aliphaticradical of at least three carbon atoms, "Q" is a divalent linking group,"M" is a cation selected from NH₄ ⁺, Na⁺, K⁺, Li⁺, H⁺ or is a protonatedalkyl amine having from 1-6 carbon atoms in the alkyl group, "A" is apolyvalent organic radical having a valency of M+p and is the residue ofa polybasic organic acid or an organic anhydride, "X" is NR (wherein Ris hydrogen or an alkyl group of from 1 to 14 carbon atoms), .Iadd.or.Iaddend.N .[.or O.]. and e, p and m are integers of 1 or 2, and (2)compatible non-ionic or anionic detergent, said detergent being waterdispersible at concentrations of at least 1% by weight and being capableof drying to a non-oily, non-tacky residue, the weight ratio of saiddetergent to said fluorochemical compound being on the order of 1:1 to2:1.
 8. The composition of claim 7 wherein said liquid vehicle compriseswater and sufficient compatible water-soluble organic solvent todissolve and/or disperse said fluorochemical compound.
 9. Thecomposition of claim 8 wherein said liquid vehicle is a mixture of waterand an alcohol selected from the group consisting of 2-butoxy ethanol,isopropyl alcohol and ethanol.
 10. The composition of claim 7 whereinsaid fluorochemical compound is ##STR23##
 11. The composition of claim10 wherein R_(f) is C₈ f₁₇ and M is K⁺, Na⁺ or NH₄ ⁺.
 12. Thecomposition of claim 7 wherein said detergent is a salt of laurylsulfate or lauryl ether sulfate.
 13. The composition of claim 7 whereinthe weight ratio of said detergent to said organic fluorochemicalcompound is on the order of 2:1.
 14. The composition of claim 1 wherein"Q" is selected from the group consisting of alkylene [--(CH₂)_(n) --],sulfonamido alkylene [--SO₂ NR(CH₂)_(n) --], alkylene carboxyloxyalkylene [--(CH₂)_(n) COOCH₂ CH₂ --], and sulfonamido alkyleneoxyalkylene [--SO₂ NR(CH₂ CH₂ O)_(n) CH₂ CH₂ --] wherein "R" is hydrogen ora lower alkyl group having from about 1 to 14 carbon atoms and n is aninteger from about 1 to 15.